Density functional studies on hydrogen‐bonded clusters of hydrogen halides and the interaction on halide anions

Abstract

Density functional theory (DFT) calculations have been performed to study the structures and stability of X Ϫ .(HX) nϭ2-5 clusters where X ϭ F, Cl, Br at B3LYP/6-311ϩϩG** level of theory. The presence of halide ions in these clusters disintegrates the hydrogen halide clusters. All the hydrogen halides are then hydrogen bonded to the centrally placed halide ions, thereby forming multiple hydrogen bonds. The interaction energies have been corrected for the basis set superposition error (BSSE) using Boy's counterpoise correction method. Evidence for the destruction of hydrogen bonds in hydrogen halide clusters due to the presence of halide ions is further obtained from topological analysis and natural bond orbital analysis. The chemical hardness and chemical potential have been calculated for all the anion clusters. The above analysis reveals that hydrogen bonding in these systems is not an essentially electrostatic interaction. The nature of the stabilization interactions operative in these multiple hydrogen-bonded clusters has been explained in terms of many-body contribution to interaction energies. From these studies, an attempt has been made to understand the nature of the molecular properties resulting from different electronegativities of the halogens.